Fluid Phase Equilibria 352 (2013) 8692

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Isobaric vaporliquid equilibrium for binary systems

of toluene + o-xylene, benzene + o-xylene, nonane + benzene
and nonane + heptane at 101.3 kPa
Bhupender S. Gupta, Ming-Jer Lee
Department of Chemical Engineering, National Taiwan University of Science and Technology, 43 Keelung Road, Section 4, Taipei 106-07, Taiwan

a r t i c l e

i n f o

Article history:
Received 2 January 2013
Received in revised form 11 April 2013
Accepted 15 May 2013
Available online 29 May 2013
Keywords:
Isobaric
VLE
o-Xylene
Nonane
Hydrocarbons

a b s t r a c t
Isobaric vaporliquid equilibrium (VLE) data for the binary systems of toluene + o-xylene, benzene + oxylene, nonane + benzene and nonane + heptane were measured at 101.3 kPa by using a modied Othmer
still. The thermodynamic consistency of these new VLE data was checked by using the point to point
test of Van Ness. No azeotrope was found in these binary systems investigated. While nonane + benzene
were found to have large positive deviation, toluene + o-xylene, benzene + o-xylene, and nonane + heptane
exhibited large negative deviation from ideal behavior. The binary interaction parameters of the Wilson,
the NRTL, the UNIQUAC models and the SRK equation of state for these four binary systems were determined through the VLE data reduction. These new VLE data were compared with the predicted values
from the UNIFAC and the COSMO-RS (conductor-like screening model for realistic solvents) models as
well. Generally, reasonable agreement was found between the predicted results and the experimental
values, except for nonane + benzene system.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Hydrocarbons are the main components in crude oils. The separation of parafns and aromatics, such as benzene (B), toluene (T)
and xylenes (X), from petroleum fractions, is commonly encountered in renery processes. Since distillation is the most popular
separation method in the chemical and petroleum industries,
vaporliquid equilibrium (VLE) data of the related mixtures are
basically important for development of the separation processes.
Although a plenty of VLE data of the mixtures containing parafns
(from C6 to C9) and aromatics (BTX) are available from literature
[114], the VLE data for some specic systems are still insufcient.
As a part of our continued studies on the isobaric VLE data measurements for the mixtures containing C6C9 and BTX [3,9], we
measured the isobaric VLE data for four binary systems, including toluene + o-xylene, benzene + o-xylene, nonane + benzene, and
nonane + heptane, at 101.3 kPa in this work. According to the results
of literature survey, no isobaric VLE data of these four binary systems at 101.3 kPa has been reported in literature. Chen et al. [8]
reported the density and the isothermal VLE data (P-T-x at 333.15 K
and 353.15 K) for nonane + benzene and toluene + o-xylene, but
they did not measure the vapor compositions (y) and thus

Corresponding author. Tel.: +886 2 2737 6626; fax: +886 2 2737 6644.
E-mail addresses: mjlee@mail.ntust.edu.tw, mjl6626@gmail.com (M.-J. Lee).
0378-3812/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.uid.2013.05.016

thermodynamic consistency test cannot be made for those VLE

data. In the present study, P-T-x-y data were measured and subsequently checked with the thermodynamic consistency test by
using the point to point test method of Van Ness [15] modied by
Fredunsland et al. [16].
In VLE data reduction, vapor phase was considered as non-ideal.
The two-term virial equation and the Hayden and OConnell (HOC)
model [17] were used to estimate the fugacity coefcient and the
second virial coefcient for each component in the vapor phase,
respectively, and the non-ideality of each liquid component were
represented by the Wilson [18], the non-random two-liquid (NRTL)
[19], and the universal quasi-chemical (UNIQUAC) [20] activity
coefcient models. These new VLE data were also correlated with
the SoaveRedlichKwong (SRK) equation of state [21]. In addition,
the predicated results from both the UNIFAC [16] and the COSMORS [22] models were also compared with these new experimental
VLE data.

2. Experimental
2.1. Materials
All the chemicals used in this study are listed in Table 1, including the suppliers and the purity levels. The purity level of each
substance has been conrmed by gas chromatography (GC) analysis. In addition, the density () and the normal boiling point

B.S. Gupta, M.-J. Lee / Fluid Phase Equilibria 352 (2013) 8692

87

Table 1
Materials description, densities () at 298.2 K and the normal boiling points (Tb ) of the pure components.a
Compound

Source

Mass fraction purity

Nonane
Benzene
Heptane
Toluene
o-Xylene

Aldrich, USA
R.D. Germany
Acros, USA
Aldrich, USA
Alfa Aesaer, USA

0.9998
0.9997
0.9998
0.9996
0.9995

/(g cm3 )

Tb /K

This work

Literature

This work

Literature

0.71407
0.87366
0.67952
0.86218
0.87566

0.71402 [23]
0.87360 [25]
0.67950 [7]
0.86219 [25]
0.87557 [7]

423.8
353.3
371.4
383.4
417.5

423.8 [24]
353.20 [26]
371.55 [7]
383.75 [25]
417.55 [7]

u() = 0.00005 g cm3 ; u(T) = 0.1 K.

(Tb ) of each compound were measured with a vibrating-tube densimeter (DMA 4500, Anton Paar, Austria) to an uncertainty of
0.00005 g cm3 and a modied Othmer VLE apparatus facilitated
with a thermocouple calibrated to an uncertainty of 0.1 K, respectively. The results are also compared with the literature values
[7,2326] in Table 1, which shows that the agreement is excellent.
No further purication has been made for the chemicals before use.
2.2. Apparatus and procedure
The VLE measurements were conducted by using an Othmerrecirculation still [27] with some modication as reported by

Johnson et al. [28]. The schematic diagram and the operating technique are similar to those reported in literature [29,30]. In each
experimental run, about 100 cm3 of freshly prepared mixture was
injected in the still and then heat was provided gradually by means
of external heater. The pressure was maintained at 101.3 0.2 kPa
during the course of measurement by a pressure adjustment system, which has been described in our previous articles [3,9]. This
pressure controlling system is composed of a graduated burrete,
directly connected with an elevation-adjustable water reservoir.
By adjusting the required water level diffrence between the burrete and the water resiorvoir, the pressure difference between local
atmospheric pressure and 101.3 kPa was compensated during each
450

450
440

(a) Toluene (1) + o-xylene (2)

440

(b) Benzene (1) + o-xylene (2)

430
430

420
410

T/K

T/K

420
410
400

400
390
380
370

390

360
380
370
0.0

350
0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

340
0.0

1.0

0.1

0.2

0.3

0.4

450

440

0.8

0.9

1.0

0.6

0.7

0.8

0.9

1.0

(d) Nonane (1) + heptane (2)

430

420

420

410

410

400

T/K

T/K

0.7

450

(c) Nonane (1) + benzene (2)

430

390
380

400
390

370

380

360

370

350
340
0.0

0.6

x1, y1

x1, y1

440

0.5

0.1

0.2

0.3

0.4

0.5

x1, y1

0.6

0.7

0.8

0.9

1.0

360
0.0

0.1

0.2

0.3

0.4

0.5

x1, y1

Fig. 1. (ad) (T, x1 or y1 ) plot for the investigated binary systems at 101.3 kPa: (), experimental liquid phase and (o); experimental vapor phase compositions; (- - -),
calculated liquid and vapor phase compositions from the Wilson model; (), calculated liquid and vapor phase compositions from the NRTL model; (), calculated liquid
and vapor phase compositions from the UNIQUAC model; (--), calculated liquid and vapor phase compositions from the SRK equation of state; (), predicted liquid and
vapor phase compositions from the UNIFAC model; (--), predicted liquid and vapor phase compositions from the COSMO-RS model.

88

B.S. Gupta, M.-J. Lee / Fluid Phase Equilibria 352 (2013) 8692

experimental run. The local atmospheric pressure was measured by

a Fortin mercury barometer (model 453, stability = 0.1 kPa, Princo
Instruments, USA).
Equilibrium state was assumed to be attained when temperature in the still reached a constant for at least 2 h. This constant
temperature was recorded. Then, the liquid samples and the
condensed vapor samples were collected (about 1 cm3 each) for
composition analysis. At least 3 replicated samples were taken for
each phase. Temperature in the still was measured with a precisely calibrated digital thermometer (TES 1310 type-K) with an
uncertainty of 0.1 K.
2.3. Analysis
The compositions of the collected samples were determined
by GC (model 8700, China Chromatography, Taiwan). This GC was
equipped with a TCD detector and a stainless-steel column (model
SE-30, Supelcoport, 80/100 mess, 14 1/8 , 20%, USA). Helium gas
with purity of 0.9995 in mass fraction was employed as a carrier
gas. Prior to the composition analysis, the calibration curves for
these binary systems should be obtained. The standard samples for
GC calibration were prepared by using an electronic balance (R&D
Model GR-200, USA) with an uncertainty of 0.1 mg. The uncertainty of compositions determination is estimated as 0.005 in
mole fraction.
3. Results and discussion
The isobaric VLE data of toluene + o-xylene and benzene + oxylene, nonane + benzene, and nonane + heptane, were measured
at 101.3 kPa. Experimental data (T, x, y) for all systems investigated along with estimated activity coefcient ( i ) are listed in
Table 2. The graphical presentation of the VLE data can be seen
from Fig. 1(ad). These graphs clearly reveal that all the systems
investigated have no azeotrope formation.
For the sake of reliability, the thermodynamic consistency
of the new VLE data were tested with the point to point test
method of van Ness et al. [15] modied by Fredunslund et al.
[16] The mean absolute deviations between calculated and experimental vapor-phase composition and saturated pressure should
be less than 0.01 and 1.33 kPa, respectively, for passing the
consistency test. From the consistency test, it is found that the deviations of vapor-phase composition are 0.0021, 0.0019, 0.0016, and
0.0015, and those of saturated pressure are 0.0079 kPa, 0.0054 kPa,
0.0050 kPa, and 0.0056 kPa for toluene + o-xylene, benzene + oxylene, nonane + benzene, and nonane + heptane, respectively. The
results indicate that all the new VLE data are passed the consistency
test.
The reported values of activity coefcients  i in Table 2 were
estimated by considering vapor phase as non-ideal, from the following equations:
yP
i = i s exp
xi Pi



Bii V Li

ij = 2Bij Bii Bjj



P Pis + (1 yi )2 Pij
RT


(1)

(2)

where xi and yi are the mole fractions of liquid and vapor phase,
respectively. P and Pis are the total pressure and the vapor pressure of pure components i, respectively. Bii , and Bjj are the second
virial coefcients of pure gases and Bij is the cross second virial
coefcient. The liquid molar volume of pure component i, V Li , was
calculated from the modied Racket equation (Yamada and Gunn

Table 2
Experimental VLE data for toluene (1) + o-xylene (2), benzene (1) + o-xylene (2),
nonane (1) + benzene (2) and nonane (1) + heptane (2) systems at 101.3 kPa.a
T/K

y1

1

2

Toluene (1) + o-xylene (2)

1.000
383.4
385.0
0.937
0.920
385.4
386.3
0.880
388.1
0.796
0.693
390.5
0.662
391.4
0.579
393.9
0.500
396.3
399.0
0.426
401.3
0.367
404.4
0.291
0.230
407.0
0.132
411.4
0.094
413.2
0.069
414.3
0.000
417.5

1.000
0.981
0.976
0.961
0.930
0.886
0.871
0.825
0.765
0.693
0.626
0.526
0.436
0.269
0.196
0.147
0.000

1.000
1.014
1.016
1.021
1.041
1.070
1.075
1.092
1.103
1.097
1.087
1.069
1.054
1.024
1.006
1.003

0.750
0.737
0.776
0.776
0.781
0.781
0.790
0.833
0.877
0.908
0.943
0.962
0.984
0.989
0.993
1.000

Benzene (1) + o-xylene (2)

353.3
1.000
353.8
0.980
354.6
0.948
355.7
0.909
356.3
0.887
357.9
0.826
0.768
359.8
0.657
363.9
0.543
368.7
0.428
375.2
0.318
383.6
384.7
0.305
387.5
0.273
0.216
393.2
401.4
0.139
0.093
406.7
410.8
0.057
413.9
0.030
0.000
417.5

1.000
0.998
0.995
0.991
0.989
0.981
0.973
0.950
0.921
0.855
0.758
0.743
0.703
0.612
0.451
0.326
0.214
0.120
0.000

1.000
1.003
1.009
1.015
1.020
1.037
1.048
1.067
1.099
1.093
1.060
1.055
1.044
1.008
0.965
0.934
0.921
0.923

0.734
0.684
0.675
0.650
0.686
0.682
0.736
0.737
0.866
0.924
0.930
0.942
0.961
0.978
0.984
0.989
0.993
1.000

Nonane (1) + benzene (2)

353.3
0.000
354.3
0.048
0.061
354.8
355.2
0.089
0.130
356.2
0.182
357.2
0.231
358.2
0.359
363.4
0.455
367.3
0.574
374.2
0.586
374.9
0.694
383.6
0.773
391.4
0.783
392.5
0.869
402.9
0.925
411.1
1.000
423.8

0.000
0.005
0.006
0.008
0.013
0.018
0.023
0.049
0.073
0.118
0.123
0.207
0.302
0.318
0.490
0.657
1.000

0.956
0.884
0.795
0.851
0.809
0.783
0.880
0.895
0.896
0.893
0.946
0.966
0.970
0.988
0.989
1.000

1.000
1.014
1.012
1.029
1.041
1.070
1.100
1.110
1.144
1.162
1.168
1.153
1.140
1.137
1.123
1.117

Nonane (1) + heptane (2)

0.000
371.4
0.071
373.3
0.163
375.7
0.249
378.7
0.367
382.3
0.420
385.1
0.534
390.3
0.641
396.2
0.722
401.6
0.802
407.5
0.830
409.6
0.883
413.9
0.902
415.5
0.957
420.0
0.965
420.7
1.000
423.8

0.000
0.010
0.027
0.050
0.084
0.117
0.176
0.274
0.375
0.506
0.560
0.675
0.720
0.867
0.891
1.000

0.628
0.680
0.744
0.753
0.837
0.840
0.909
0.943
0.969
0.978
0.986
0.987
0.997
0.998
1.000

1.000
1.015
1.037
1.041
1.084
1.062
1.084
1.076
1.056
1.029
1.020
1.000
0.995
0.984
0.977

x1

u(T) = 0.1 K; u(x1 ) = 0.005; u(y1 ) = 0.005; u( 1 ) = 0005.

B.S. Gupta, M.-J. Lee / Fluid Phase Equilibria 352 (2013) 8692
1.5

1.5

(a) Toluene (1) + o-xylene (2)

(b) Benzene(1) + o-xylene (2)

1.0

1, 2

1, 2

89

0.5
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0.5
0.0

1.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0.6

0.7

0.8

0.9

1.0

x1

x1
2.0

1.5

(c) Nonane (1) + benzene (2)

(d) Nonane (1) + heptane (2)

1, 2

1, 2

1.5

1.0

1.0

0.5
0.0

0.1

0.2

0.3

0.4

0.5

x1

0.6

0.7

0.8

0.9

0.5
0.0

1.0

0.1

0.2

0.3

0.4

0.5

x1

Fig. 2. (ad) ( 1 ,  2 versus x1 ) plot for the investigated binary systems at 101.3 kPa: (o); experimental activity coefcient of component 1 in the binary mixture; (),
experimental activity coefcient of component 2 in the binary mixture; (- - -), calculated activity coefcients from the Wilson model; (), calculated activity coefcients from
the NRTL model; (), calculated activity coefcients from the UNIQUAC model; (), predicted activity coefcients from the COSMO-RS model; (), predicted activity
coefcients from the UNIFAC model.

[31]). The vapor pressure of pure component i was calculated from

the extended Antoine equation:
ln(Pis ) = A1 +

B2
+ D4 T + E5 ln T + F6 T G7
T + C3

(3)

=


 2
np  calc
exp t

P
P
k=1

where Pis is in kPa and T in K. The coefcients A1 to G7 for each component were taken from Aspen Plus physical property databanks
and reported in Table 3. The self and cross second virial coefcients
were calculated by using Hayden and OConnell model [17], which
involves the following terms:
B = Bfreenonpolar + Bfreepolar + BmetasTable + Bbound + Bchem

was adopted for the data reduction.

(4)

Since no association effect was expected in these binary systems investigated, Bchem term was vanished in the virial coefcient
calculation. The physical properties of each component required in
the calculation of the second virial coefcients given in Table 4.
The experimental VLE data are correlated with the activity coefcient model, the Wilson, the NRTL, or the UNIQUAC, for liquid
phase and the two-term virial equation for vapor phase. The value
of ij in the NRTL model was xed to 0.3 and the parameters of the
UNIQUAC model (r and q) are also given in Table 4. The following
objective function (), based on the maximum-likelihood principle,


+

p
exp t

calc x
x1,k
1,k

x1

 2


+


+

exp t

Tkcalc Tk

 2

T
exp t

calc y
y1,k
1,k

y1

 2

(5)

where np is the number of data points. The superscripts of calc. and

expt. denote the calculated and the experimental values, respectively. The standard deviations of temperature ( T ), pressure ( P ),
liquid composition ( x ), and vapor composition ( y ) are 0.1 K,
0.2 kPa, 0.005, and 0.005, respectively. By using this objective function, the uncertainties of all measured variables are considered
simultaneously and the determined optimal values of the model
parameters are much more statistically sound.
The measured VLE data were also correlated with the
SoaveRedlichKwong (SRK) equation of state. The results of correlation presented in Fig. 1(ad). This equation is applicable to
nonpolar and slightly polar components. For calculating mixture
properties, the SRK equation of state with the invariant asymmetric

90

B.S. Gupta, M.-J. Lee / Fluid Phase Equilibria 352 (2013) 8692

Table 3
Parameters of the extended Antoine equationa , b for pure compounds.
Compound

A1

Nonane
Heptane
Benzene
Toluene
o-Xylene
a
b

102.44
80.92
76.19
70.03
83.49

B2

C3

9030.40
6996.40
6486.20
6729.80
7955.20

0
0
0
0
0

D4

E5

F6
6

12.88
9.88
9.21
8.17
10.08

0
0
0
0
0

7.85 10
7.21 106
6.98 106
5.30 106
5.95 106

G7

T1 /K

T2 /K

2.0
2.0
2.0
2.0
2.0

219.66
182.57
278.68
178.18
247.98

594.60
540.20
562.05
591.75
630.30

Taken from Aspen Plus physical property databanks.

B
Extended Antoine equation: ln(P S ) = A1 + T +C2 + D4 T + E5 ln T + F6 T G7 for T1 < T < T2 , where PS is in kPa and T in K.
3

Table 4
Physical properties and parameters of the UNIQUAC model for pure components.
Compound

Tc a /K

Pc a /kPa

Vc a /(cm3 mol1 )

a /debye

Zc a

ra

qa

Nonane
Heptane
Benzene
Toluene
o-Xylene

594.60
540.20
562.05
591.75
630.30

2290
2740
4895
4108
3732

551
428
256
316
370

0
0
0
0.3597
0.6295

0.255
0.268
0.261
0.264
0.264

0.4435
0.3495
0.2103
0.2640
0.3101

5.476
5.174
3.190
2.968
4.658

6.523
4.396
2.400
3.923
3.536

Taken from Aspen Plus physical properties databanks.

mixing rule of Mathias et al. [32] was used in this study. The model
is dened as
P=

a
RT

V b
V (V + b)

(6)

with
bm =

c


xi bi

(7)

i=1

am = a(0) + a(1)

(8)

where
a(0) =

c
c



xi xj

ai aj (1 kij ); kij = kji

(9)

i=1 j=1

a(1) =

c


xi

c


i=1

3
xj ((ai aj ))1/2 lji )

1/3

; lij =/ lji

The calculated activity coefcients ( i ) from the correlative

models (the Wilson, the NRTL, and the UNIQUAC) and the predictive models (the COSMO-RS and the UNIFAC) are compared with
the experimental values in Fig. 2(ad). Again, the NRTL model
represents satisfactorily of the activity coefcients varying with
composition for all systems investigated.
To assess the non-ideality of these investigated systems, we
calculated the excess Gibbs free energies GE from the following
equation:
GE = RT (x1 ln 1 + x2 ln 2 )

where the activity coefcients,  i , were calculated from the NRTL

model with the binary parameters as given in Table 5. The variations
of the experimental and the calculated excess Gibbs free energies
(GE /R) with liquid composition for the systems investigated are
presented in Fig. 3. The binary system of nonane + benzene was
found to have large positive deviations, while toluene + o-xylene,

(10)

j=1

70

The binary interaction parameter kij was treated as a

temperature-dependent function:

50

(02)

+ kij
T

(11)

For a binary system, there are four binary interaction parame(01)

(02)
ters, kij , kij , lij , and lji . The optimal values of these parameters
were determined by tting the binary VLE data to the above dened
equation of state.
The optimal values of binary interaction parameters of the activity coefcient models (the Wilson, the NRTL, and the UNIQUAC), the
SRK equation of state and the root mean square deviations (RMSD)
of the data correlation are reported in Table 5. In addition, the
new VLE data are also compared with the predicted results from
two predictive models: the UNIFAC and the COSMO-RS, as given
in Table 5. The comparisons of the calculated values with experimental data are illustrated in Fig. 1(ad). As seen from this graph
and the RMSD values tabulated in Table 5, we found that all three
activity coefcient models and the SRK equation of state correlated
well for all binary systems investigated. In general, the NRTL model
yields the best results. We also found that reasonable results were
obtained from two predictive models, the UNIFAC and the COSMORS. However, the COSMO-RS fails to quantitatively predict the VLE
properties of nonane + benzene.

40

kij =

60

(G /R)/K

(01)

kij

(12)

30
20
10
0
-10
-20
0.0

0.1

0.2

0.3

0.4

0.5

x1

0.6

0.7

0.8

0.9

1.0

Fig. 3. Plot of experimental excess Gibbs free energies at 101.3 kPa and the calculated values from the NRTL model against mole fraction; (), experimental excess
Gibbs free energy of toluene (1) + o-xylene (2); (), experimental excess Gibbs free
energy of benzene (1) + o-xylene (2); (o), experimental excess Gibbs free energy
of nonane (1) + benzene (2); (), experimental excess Gibbs free energy of nonane
(1) + heptane (2); (), calculated excess Gibbs free energy of toluene (1) + o-xylene
(2); (), calculated excess Gibbs free energy of benzene (1) + o-xylene (2); (), calculated excess Gibbs free energy of nonane (1) + benzene (2); and (), calculated
excess Gibbs free energy of nonane (1) + benzene (2).

B.S. Gupta, M.-J. Lee / Fluid Phase Equilibria 352 (2013) 8692

91

Table 5
Optimal binary interaction parameters and root mean square deviation (RMSD) for variables (T, P, x1 and y1 ).
Model

Parameters

Toluene (1) + o-xylene (2)

M12 = 0.43
Wilsonb
M21 = 23.75
D12 = 24.48
NRTLc
D21 = 6.96
P12 = 29.59
UNIQUACd
P21 = 0.72
(01)
k12 = 0.94
SRKe

N12 /K = 596.01
N21 /K = 8196.45
E12 /K = 8158.08
E21 /K = 3396.29
Q12 /K = 10693.7
Q21 /K = 119.24
l12 = 0.05
l21 = 0.12

(02)

k12 = 0.002

UNIFACf
COSMO-RSf

Benzene (1) + o-xylene (2)

Wilsonb
M12 = 2.44
M21 = 27.97
NRTLc
D12 = 25.57
D21 = 3.31
d
P12 = 15.11
UNIQUAC
P21 = 2.03
(01)
k12 = 0.30
SRKe

N12 /K = 534.41
N21 /K = 9304.69
E12 /K = 7971.53
E21 /K = 1835.54
Q12 /K = 4870.50
Q21 /K = 421.44
l12 = 0.07
l21 = 0.07

(02)

k12 = 0.001

UNIFACf
COSMO-RSf

Nonane (1) + benzene (2)

M12 = 18.42
Wilsonb
M21 = 1.42
c
D12 = 2.71
NRTL
D21 = 15.75
P12 = 1.93
UNIQUACd
P21 = 10.79
(01)
k12 = 0.41
SRKe

N12 /K = 5721.16
N21 /K = 202.62
E12 /K = 1556.45
E21 /K = 4386.76
Q12 /K = 442.95
Q21 /K = 3412.33
l12 = 0.10
l21 = 0.05

(02)

k12 = 0.001

UNIFACf
COSMO-RSf

Nonane (1) + heptane (2)

Wilsonb
M12 = 28.80
M21 = 0.80
D12 = 4.45
NRTLc
D21 = 20.83
d
P12 = 1.26
UNIQUAC
P21 = 14.68
(01)
k12 = 0.59
SRKe

N12 /K = 9916.22
N21 /K = 106.49
E12 /K = 6559.22
E21 /K = 2365.51
Q12 /K = 121.46
Q21 /K = 4905.53
l12 = 0.08
l21 = 0.08

(02)

k12 = 0.002

UNIFACf
COSMO-RSf

RMSD M =

1
np

np



Mkcalc

exp t
Mk

2

0.5

RMSD Ta /K

RMSD Pa /kPa

RMSD x1 a

RMSD y1 a

0.17

0.019

0.009

0.010

0.13

0.015

0.002

0.003

0.14

0.015

0.004

0.005

0.26

0.029

0.003

0.002

0.72
0.51

0.034
0.026

0.06

0.007

0.004

0.009

0.06

0.006

0.002

0.003

0.05

0.006

0.004

0.007

0.10

0.011

0.003

0.004

1.80
1.11

0.023
0.018

0.08

0.008

0.004

0.007

0.07

0.007

0.004

0.002

0.09

0.008

0.004

0.005

0.11

0.011

0.004

0.003

0.82
3.35

0.012
0.037

0.08

0.008

0.006

0.010

0.07

0.007

0.003

0.002

0.07

0.006

0.004

0.003

0.09

0.010

0.003

0.002

1.01
0.63

0.022
0.015

, where np is the number of data points and M represents T, P, x1 or y1 .

k=1
b
c
d
e

Wilson model: lnAij = [Mij + Nij /T].

NRTL model: ij = [Dij + Eij /T]. The value of was xed to be 0.3 for each binary system.
UNIQUAC model: ij = [exp(Pij + Qij /T)].
SRK :

kij = kij01 + kij02 /T , kij = kji

lij =
/ 1ji
The RMSDs from two predictive models, the UNIFAC and the COSMO-RS, were obtained via the Bubble-T VLE calculation, in which the experimental pressure and liquid
composition are given and thus no RMSDs of P and x1 are reported.
f

benzene + o-xylene, and nonane + heptane systems exhibit negative deviations from Raoults law.
4. Conclusions
Isobaric VLE data have been measured for four binary systems, toluene + o-xylene, benzene + o-xylene, nonane + benzene,
and nonane + heptane, at 101.3 kPa. No azeotrope was formed
in these four systems investigated. All the VLE data passed the
thermodynamic consistency test. These experimental VLE data
were correlated well by using the Wilson-HOC, the NRTL-HOC,
the UNIQUAC-HOC models and the SRK equation of state. The
NRTL model yields the best results. While nonane + benzene system

exhibits large positive deviations, toluene + o-xylene, benzene + oxylene, and nonane + heptane systems show negative deviations
from the Raoults law. This study also found that the UNIFAC and
the COSMO-RS predict the VLE properties of the systems investigated fairly well. However, the COSMOS-RS failed to quantitatively
estimate the VLE behavior of nonane + benzene system.
List of symbols

a
A1 G7
B

b constants in the SRK equation.

coefcients of the extended Antoine equation
second virial coefcient (cm3 mol1 )

92

c
Dij , Eij
G
kij ,
Mij , Nij
np
P
Pij , Qij
q
r
R
T
u
V
x
y
Z

B.S. Gupta, M.-J. Lee / Fluid Phase Equilibria 352 (2013) 8692

number of components
parameters of the NRTL model
Gibbs free energy (J mol1 )
lij parameters of the SRK equation
parameters of the Wilson activity coefcient models
number of data points
pressure (kPa)
parameters of the UNIQUAC model
surface area parameter of the UNIQUAC model
volume parameter of the UNIQUAC model
gas constant (J mol1 K1 )
temperature (K)
uncertainty
molar volume (cm3 mol1 )
mole fraction in liquid phase
mole fraction in vapor phase
compressibility factor

Greek letters

non-randomness parameter of the NRTL model


activity coefcient
dipole moment (debye)


objective function

density (g cm3 )

standard deviation

acentric factor
Subscripts
b
normal boiling
critical property
c
i, j
components i and j
ij
ij pair interaction
m
mixture
Superscripts
calc
calculated value
expt
experimental value
E
excess property
saturation
S
Funding
The authors gratefully acknowledge the nancial support from
the National Science Council, Taiwan, through Grant No. NSC1022218-E002-006 and scholarship from National Taiwan University
of Science & Technology.

Acknowledgement
The authors thank to Dr. Ho-mu Lin for valuable discussions.
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